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Cross-linked Electrospun gel polymer electrolytes for Lithium-Ion Batteries

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CHINESE JOURNAL OF polymer SCIENCE 2024年第8期42卷 1021-1028页

作者： Gong, Xue Xiao, Qin Li, Qing-Yin Liang, Wen-Cui Chen, Feng Li, Long-Yu Ren, Shi-Jie Sichuan Univ Coll Polymer Sci & Engn State Key Lab Polymer Mat Engn Chengdu 610065 Peoples R China

Lithium-ion batteries (LIBs) benefit from an effective electrolyte system design in both terms of their safety and energy storage capability. Herein, a series of precursor membranes with high porosity were produced using electrospinning technology by mixing PVDF and triblock copolymer (PS-PEO-PS), resulting in a porous structure with good interconnections, which facilitates the absorbency of a large amount of electrolyte and further increases the ionic conductivity of gel polymer electrolytes (GPEs). It has been demonstrated that post-cross-linking of the precursor membranes increases the rigidity of the nanofibers, which allows the polymer film to be dimensionally stable up to 260 degrees C while maintaining superior electrochemical properties. The obtained cross-linked GPEs (CGPEs) showed high ionic conductivity up to 4.53x10-3 Scm-1. With the CGPE-25, the assembled Li/LiFePO4 half cells exhibited good rate capability and maintained a capacity of 99.4% and a coulombic efficiency of 99.3% at 0.1 C. These results suggest that the combination of electrospinning technique and post-cross-linking is an effective method to construct polymer electrolytes with high thermal stability and steadily decent electrochemical performance, particularly useful for Lithium-ion battery applications that require high-temperature usage.

关键词： Electrospinning Cross-linked gel polymer electrolytes Lithium-ion batteries MEMBRANE SEPARATOR STABILITY SIO2

gelation mechanisms of gel polymer electrolytes for zinc-based batteries

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Chinese Chemical Letters 2024年第5期35卷 97-116页

作者： Mengjun Sun Zhi Wang Jvhui Jiang Xiaobing Wang Chuang Yu Collaborative Innovation Center of Henan Province for Green Manufacturing of Fine Chemicals Key Laboratory of Green Chemical Media and ReactionsMinistry of EducationSchool of Chemistry and Chemical EngineeringHenan Normal UniversityXinxiang 453007China Key Laboratory for Yellow River and Huaihe River Water Environment and Pollution Control Ministry of EducationHenan Key Laboratory for Environmental Pollution ControlSchool of EnvironmentHenan Normal UniversityXinxiang 453007China State Key Laboratory of Advanced Electromagnetic Engineering and Technology School of Electrical and Electronic EngineeringHuazhong University of Science and TechnologyWuhan 430074China

Zinc-based batteries(ZBs)have been deemed as a potential substitute for lithium-ion batteries due to its unique advantages of abundant resources,low cost and acceptable energy *** great progress in designing electrode materials has been made,the development of high-performance ZBs still remain challenges,such as the dendrite growth of zinc anode,hydrogen evolution reaction,limited electrochemical stability window,water evaporation and liquid *** polymer electrolytes(GPEs),including hydrous GPEs with low content of active water and anhydrous GPEs without the presence of water,are proposed to avoid these ***,employing GPEs is conductive to fabricate flexible devices owing to the good mechanical *** date,most of researches focus on discovering new GPEs and exploring its application on flexible or wearable *** reviews also have outlined the polymer matrixes and advances of GPEs in various battery *** this,herein,we seek to summarize the gelation mechanisms of GPEs,involving physical gel of polymer,chemical crosslinking of polymer and chemical polymerization of ***,the preparation methods are also *** addition,not only the features and central conundrum of GPEs are analyzed but also the corresponding strategies are discussed,contributing to design GPEs with ideal properties for high-performance ZBs.

关键词： gelation mechanisms gel polymer electrolytes Zinc-based batteries gelation methods

Research progress on gel polymer electrolytes for lithium-sulfur batteries

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Journal of Energy Chemistry 2021年第5期30卷 420-437页

作者： Jie Qian Biyu Jin Yuanyuan Li Xiaoli Zhan Yang Hou Qinghua Zhang College of Chemical and Biological Engineering Zhejiang UniversityHangzhou 310027ZhejiangChina Institute of Zhejiang University-Quzhou Quzhou 324000ZhejiangChina

Lithium-sulfur(Li-S)batteries have become a promising candidate for advanced energy storage system owing to low cost and high theoretical specific *** the last decade,in pursuit of Li-S batteries with enhanced safety and energy density,the investigation on the electrolytes has leaped form liquid organic electrolytes to solid polymer ***,such solid-state Li-S battery system is greatly limited by unfavorable ionic conductivity,poor interfacial contact and narrow electrochemical windows on account of the absence of any liquid *** address these issues,gel polymer electrolytes(GPEs),the incorporation of liquid electrolytes into solid polymer matrixes,have been newly *** the excellent ionic transport and low interfacial resistance provided by GPEs have prompted numerous researchers to make certain progress on high-performance Li-S coins,a comprehensive review on GPEs for Li-S batteries remains ***,this review focuses on recent development and progress on GPEs in view of their physical and chemical properties for the applications in Li-S *** on the components including solid hosts,liquid solutions and fillers of GPEs are systematically summarized with particular emphasis on the relationship between components and ***,current challenges and directional outlook for fabricating GPEs-based Li-S batteries with outstanding performance are outlined.

关键词： Lithium-sulfur batteries gel polymer electrolytes Solid hosts Liquid solutions

PREPARATION OF STAR NETWORK PEG-BASED gel polymer electrolytes FOR ELECTROCHROMIC DEVICES

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Chinese Journal of polymer Science 2008年第1期26卷 91-97页

作者： Gong, Yong-feng Fu, Xiang-kai Zhang, Shu-peng Jiang, Qing-Long SW Univ Coll Chem & Chem Engn Res Inst Appl Chem Chongqing 400715 Peoples R China Key Lab Appl Chem Chongqing Municipal Chongqing 400715 Peoples R China Minist Educ Key Lab Ecoenvironm Gorges Reservoir Reg 3 Chongqing 400715 Peoples R China

An amorphous,colorless,and highly transparent star network polymer with a pentaerythritol core linking four PEG-block polymeric arms was synthesized from the poly(ethylene glycol)(PEG),pentaerythritol,and dichloromethane by Williamson *** and ~1H-NMR measurement demonstrated that the polymer repeating units were C[CH_2-OCH_2O-(CH_2CH_2O)_m-CH_2O-(CH_2CH_2O)_n-CH_2O]_*** polymer host held well mechanical properties for pentaerythritol *** gel polymer electrolytes based on Lithium pe...

关键词： Ionic conductivity Star network polymer gel polymer electrolytes Electrochromic devices

Bifunctional TiO_(2-x)nanofibers enhanced gel polymer electrolyte for high performance lithium metal batteries

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Journal of Energy Chemistry 2024年第2期89卷 437-448,I0011页

作者： Yixin Wu Zhen Chen Yang Wang Yu Li Chunxing Zhang Yihui Zhu Ziyu Yue Xin Liu Minghua Chen Key Laboratory of Engineering Dielectric and Applications(Ministry of Education) School of Electrical and Electronic EngineeringHarbin University of Science and TechnologyHarbin 150080HeilongjiangChina

Exploration of advanced gel polymer electrolytes(GPEs)represents a viable strategy for mitigating dendritic lithium(Li)growth,which is crucial in ensuring the safe operation of high energy density Li metal batteries(LMBs).Despite this,the application of GPEs is still hindered by inadequate ionic conductivity,low Li^(+)transference number,and subpar physicochemical ***,Ti O_(2-x)nanofibers(NF)with oxygen vacancy defects were synthesized by a one-step process as inorganic fillers to enhance the thermal/mechanical/ionic-transportation performances of composite *** characterizations and theoretical calculations reveal that the oxygen vacancies on the surface of Ti O_(2-x)NF accelerate the dissociation of Li PF_6,promote the rapid transfer of free Li^(+),and influence the formation of Li F-enriched solid electrolyte ***,the composite GPEs demonstrate enhanced ionic conductivity(1.90m S cm^(-1)at room temperature),higher lithium-ion transference number(0.70),wider electrochemical stability window(5.50 V),superior mechanical strength,excellent thermal stability(210℃),and improved compatibility with lithium,resulting in superior cycling stability and rate performance in both Li||Li,Li||Li Fe PO_(4),and Li||Li Ni_(0.8)Co_(0.1)Mn_(0.1)O_(2)***,the synergistic influence of nanofiber morphology and enriched oxygen vacancy structure of fillers on electrochemical properties of composite GPEs is comprehensively investigated,thus,it is anticipated to shed new light on designing high-performance GPEs LMBs.

关键词： Nanofibers fillers Oxygen vacancies gel polymer electrolytes Lithium metal batteries

Interpenetrating network-reinforced gel polymer electrolyte for ultra-stable lithium−iodine batteries

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Carbon Energy 2024年第6期6卷 234-247页

作者： Ying Jiang Peng Huang Minman Tong Bingxin Qi Tao Sun Zhongyun Xian Wen Yan Chao Lai School of Chemistry and Materials Science Jiangsu Normal UniversityXuzhouJiangsuChina

Li-I2 batteries have attracted much interest due to their high capacity,exceptional rate performance,and low *** so,the problems of unstable Li anode/electrolyte interface and severe polyiodide shuttle in Li-I2 batteries need to be ***,the interfacial reactions on the Li anode and I2 cathode have been effectively optimized by employing a well-designed gel polymer electrolyte strengthened by cross-linked Ti-O/Si-O(GPETS).The interpenetrating network-reinforced GPETS with high ionic conductivity(1.88×10^(-3)S cm^(-1)at 25℃)and high mechanical strength endows uniform Li deposition/stripping over 1800 h(at 1.0mA cm^(-2),with a plating capacity of 3.0mAh cm^(-2)).Moreover,the GPETS abundant in surface hydroxyls is capable of capturing soluble polyiodides at the interface and accelerating their conversion kinetics,thus synergistically mitigating the shuttle *** from these properties,the use of GPETS results in a high capacity of 207 mAh g^(-1)(1 C)and an ultra-low fading rate of 0.013%per cycle over 2000 cycles(5 C).The current study provides new insights into advanced electrolytes for Li-I2 batteries.

关键词： electrode/electrolyte interface gel polymer electrolytes lithium dendrites lithium−iodine batteries polyiodide shuttle

Crosslinked solubilizer enables nitrate-enriched carbonate polymer electrolytes for stable,high-voltage lithium metal batteries

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Science Bulletin 2024年第2期69卷 209-217页

作者： Chuyang Jing Kuan Dai Dong Liu Wenran Wang Libao Chen Chunxiao Zhang Weifeng Wei State Key Laboratory of Powder Metallurgy Central South UniversityChangsha 410083China College of Materials and Chemical Engineering Hunan Institute of EngineeringXiangtan 411104China

High-voltage lithium metal batteries(LMBs)have been considered promising next-generation highenergy-density ***,commercial carbonate electrolytes can scarcely be employed in LMBs owing to their poor compatibility with metallic lithium.N,N-dimethylacrylamide(DMAA)-a crosslinkable solubilizer with a high Gutmann donor number-is employed to facilitate the dissolution of insoluble lithium nitrate(LiNO3)in carbonate-based electrolytes and to form gel polymer electrolytes(GPEs)through in situ *** Lit solvation structure of the GPEs is regulated using LiNO3 and DMAA,which suppresses the decomposition of LiPFe and facilitates the formation of an inorganic-rich solid electrolyte ***,the Coulombic efficiency(CE)of the LillCu cell assembled with a GPE increases to 98.5%at room temperature,and the high-voltage LillNCM622 cell achieves a capacity retention of 80.1%with a high CE of 99.5%after 400 *** bifunctional polymer electrolytes are anticipated to pave the way for next-generation high-voltage LMBs.

关键词： Crosslinked solubilizer Lithium nitrate Carbonate electrolytes gel polymer electrolytes Lithium metal batteries

A self-standing,UV-cured semi-interpenetrating polymer network reinforced composite gel electrolytes for dendrite-suppressing lithium ion batteries

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Journal of Materiomics 2019年第2期5卷 185-194页

作者： Ruiping Liu Zirui Wu Peng He Haoyu Fan Zeya Huang Lei Zhang Xinshuang Chang Hang Liu Chang-an Wang Yutao Li Department of Materials Science and Engineering China University of Mining&Technology(Beijing)Beijing 100083China School of Materials Science and Engineering State Key Laboratory of New Ceramics and Fine ProcessingTsinghua UniversityBeijing 100084China Department of Mechanical Engineering University of Alaska FairbanksFairbanksAK 99775United States Materials Science and Engineering Program and Texas Materials Institute The University of Texas at AustinTexas78712United States

A self-standing,flexible and lithium dendrite growth-suppressing composite gel polymer electrolyte membrane was designed for the use of room-temperature lithium ion *** multi-functional composite semi-interpenetrating polymer network(referred to as“Cs-IPN”)electrolyte membrane was fabricated by combining a UV-cured ethoxylated trimethylolpropane triacrylate(ETPTA)macromer with alumina nanoparticles in the presence of liquid electrolyte and thermoplastic linear poly(ethylene oxide)(PEO).The polymer electrolyte membrane exhibits a semi-interpenetrating polymer network structure and a higher room temperature ionic conductivity,which impart the electrolyte with a significant cycling(120 mAh g^(-1)after 200 cycles)and a remarkable rate(137 mAh g^(-1)at 0.1℃,130 mAh g^(-1)at 0.5℃,119 mAh g^(-1)at 1℃ and 100 mAh g^(-1)at 2℃)performance in Li/LiFePO4 *** importantly,the polymer electrolyte possesses superior ability to inhibit the growth of lithium dendrites,which makes it promising for next generation lithium ion batteries.

关键词： gel polymer electrolytes Semi-interpenetrating polymer network UV-Cured reaction Ionic conductivity Lithium ion batteries

Thiol-ene crosslinked cellulose-based gel polymer electrolyte with good structural integrity for high cycling performance lithium-metal battery

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Chinese Chemical Letters 2023年第4期34卷 283-289页

作者： Hongbing Zhang Sijie Wang Yujie Wang Shuhan Dong Wen Chen De Li Feng Yu Yong Chen State Key Laboratory of Marine Resource Utilization in South China Sea Hainan Provincial Key Laboratory of Research on Utilization of Si-Zr-Ti ResourcesHainan UniversityHaikou 570228China Guangdong Key Laboratory for Hydrogen Energy Technologies School of Materials Science and Hydrogen EnergyFoshan UniversityFoshan 528000China

gel polymer electrolytes(GPEs) are considered to be one most promising alternative to liquid electrolytes due to their suitability for creating safe and durable solid-state lithium-metal batteries. However, the mechanical properties of GPEs usually deteriorate dramatically when polymer matrices are plasticized by a liquid electrolyte, which leads to significant loss of battery performance. Therefore, the long-term structural integrity and good mechanical strength are critical characteristics of GPEs designed for highperformance batteries. Here, an ecologically compatible cellulose-based GPE with a crosslinked structure is synthesized via a facile and effective thiol-ene click chemistry method. The prepared thiol-ene crosslinked GPE possesses enhanced mechanical strength(10.95 MPa) and rigid structure, which enabled us to fabricate Li Fe PO_(4)|Li batteries with ultra-long cycling performance. The capacity retention of the crosslinked cellulose-based GPE can be up to 84% at 0.5 C, even after 350 cycles, which is considerably higher than that of non-crosslinked GPE for which rapid decline in capacity occurs after 200 cycles. In addition, a GPE preparation method described in this work compares favorably well with existing commercial electrolytes for lithium metal batteries.

关键词： gel polymer electrolytes Cellulose Crosslinked network Thiol-ene click chemistry Lithium-metal battery